Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

• This invention relates to a mixture of (1) an incompletely condensed organopolysiloxane resin modified with a diorganodiacycloxysilane to eliminate essentially all silicon-bonded hydroxyl groups and (2) a monoorganotriacyloxysilane.
• the principal object of this invention is to produce an organosilicon resin coating composition employing as a curing agent a monoorganotriacyloxysilane, which coating composition neither gels nor skins on standing in a closed container but which cures within 24 hours in air at room temperature when applied as a coating to wood, plastic, metal and ceramic surfaces.
• This invention relates specifically to an essentially hydroxyl-free organopolysiloxane resin containing siliconbonded acyloxy radicals of less than four carbon atoms, said radicals being present in ratios ranging from one per 100 silicon atoms to one per three silicon atoms.
• essentially hydroxyl-free means that the resin contains no detectable amount of silicon-bonded OH groups. If the resin does contain an appreciable amount of such groups, it is not stable to gelation at room temperature, especially when mixed with the triacyloxysilane hereinafter described.
• Such a composition is prepared by heating preferably in the range of from 75-150 C. 1) an organopolysiloxane resin having in the vicinity of from '1 to 33.3 mol percent silicon-bonded hydroxyl and/or alkoxyl groups, e.g.
• methoxyl and ethoxyl groups and having per silicon atom from 1.1 to 1.7 monovalent hydrocarbon radicals of which preferably from 0.25 to 1.0 radical per silicon is phenyl with v(2) a carboxylic acid of less than four carbon atoms or its anhydride or a diorganodiacyloxysilane, the acyl radicals of which contain less than four carbon atoms in a ratio suflicient to produce an essentially hydroxyl-free resin containing'from 1 to 33.3 acyloxy groups per 100 silicon atoms.
• the by-products are distilled off.
• the best method is to react a diorganodiacyloxysilane with a hydroxylated siloxane resin.
• the organic radicals on silicon of the essentially hydroxyl-free siloxane resin are limited as a practical matter to the phenyl radical and aliphatic hydrocarbon radicals of less than 7 carbon atoms, such as methyl, ethyl, propyl, butyl, amyl, hexyl, vinyl, and allyl and their isomers.
• the organic radicals can be any monovalent hydrocarbon radicals.
• the presence of the phenyl radical in an amount equal tofrom .25 to 1 phenyl radical per silicon atom improves the weatherability of the ultimate coating over non-phenyl resins.
• any resin mixture will be such that there is an average of .25 to 1 phenyl radical per silicon atom in the mixture even though a non-phenyl resin can be included in the mixture.
• the acyl radicals attached to the silane-silicon through a SiOC linkage can have from 1 to 3 carbon atoms, e.g. formyl, acetyl and propionyl.
• Examplesof diorganodiacyloxysilanes which are operative in preparing the compositions of this invention include Ph- Si(OAc) EtPhSi(OAc) Me Si(OOCH) M (C1oH21)Si(OAC)2, (Cyclic- C H iso-PrSi (OOCCH CH OOCH) (C H13)2Sl(OAC)2, (CyC1ic-C5H1o)2Sl(OAC) 2, and (cyclic- C H )PhSi(OAc) Mixtures of these silanes are also operative.
• the abbreviations used herein are those in common practice in Chemical Abstracts and are defined as follows: Me-methyl, Etethyl, Pr--propyl, Bubutyl, Ph--phenyl and Ac-acetyl.
• acylation of the hydroxylated-alkoxylated resin is most easily done in the presence of a solvent, e.g. xylene, which is inert to both the resin and the acylating agent.
• a solvent e.g. xylene
• the replacement of all of the silicon-bonded hydroxyl groups, if any, originally present in the resin with acyloxy radicals together with the introduction into the resin of acyloxy radicals within the limits of the claims produces v a resin essentially inactive by itself but which, when mixed with certain monoorganotriacyloxysilanes, has very good shelf life and yet is sufliciently active to form a cured coating within 24 hours at room temperature in air.
• This invention also relates then to a mixture of the above-described acyloxated organopolysiloxane with a monohydrocarbotriacyloxysilane in which each hydrocarbon radical contains less than four carbon atoms and eachacyloxy radical contains less than four carbon atoms.
• the monoorganotriacyloxysilane cancontain any monovalent hydrocarbon of from 1 to 3 carbon atoms, e.g. methyl, ethyl, vinyl, propyl, and their isomers.
• the acyloxy radicals can be any of those described above.
• Examples of operative monoorganotriacyloxysilanes include MeSi(OAc) EtSi(OAc) PrSi(OOCH) 3 and C H Si(OOCCI-I CH (OOCH) 2
• the operative monoorganotriacyloxysilanes can be employed individually or in mixtures and can be added as solids or in solution in an inert solvent, e.g. toluene.
• the amount of monoorganotriacyloxysilane which must be added to the stabilized acyloxated organopolysiloxane resins of this invention to facilitate curing is not critical. However, less than 0.5 molecule of the silane per siloxanesilicon-bonded acyloxy group gives negligible results. More than 3 molecules of silane per siloxane-siliconbonded acyloxy group is unnecessary.
• the diorganodiacyloxysilanes and monoorganotriacyloxysilanes employed in this invention are prepared by reacting the corresponding chlorosilanes with the desired carboxylic acid or its anhydride or'an alkali metal salt thereof.
• This type of reaction is well known in the art as is the preparation of the desired chlorosilanes by the addition of organic radicals to silicon tetrachloride or trichlorosilane by the use of a Grignard reagent or the addition of an unsaturated compound to silicon-bonded hydrogen as in trichlorosilane or a monoorganodichlorosilane.
• compositions of this invention there is no criticality in the presence or absence of inert solvents at any step.
• solvents which can be used in preparing and using the compositions of this invention include benzene, toluene, xylene, perchloroethylene, ohlorobenzene, dibutylether and methylisobutylketone.
• the stabilized acyloxated organopolysiloxanes of this invention have excellent shelf life.
• the mixture compositions of this invention will neither gel nor skin after standing long periods of time in a closed container, but upon being exposed to air as in a coating application on, for example, wood, metal, ceramic, glass or plastic surfaces, these compositions can be easily cured by mere air-drying atv room temperature.
• Additives such as pigments, antioxidants, ultraviolet absorbents and the like can be included in the compositions of this invention.
• resin A is a copolymer of- 55 mol percent phenylmethylsiloxane units, 30 mol percent monomethylsiloxane units and 15 mol percent monophenylsiloxane units and contain-s one silicon-bonded hydroxyl group per 14.7 silicon atoms.
• Resin B is a copolymer of 31.4 mol percent phenylmethylsiloxane units, 34 mol percent monomethylsiloxane units and 34.6 mol percent monophenylsiloxane units and contains one silicon-bonded hydroxyl group per 21.9 silicon atoms.
• Example 1 Fifty grams of resin A and 50 grams of resin B, each added as a 50% by weight solution in xylene, were mixed with 8.8 grams of dimethyldiacetoxysilane (equivalent to one molecule of silane per silicon-bonded hydroxyl group). This mixture was refluxed for 20 minutes, after which 22 ml. of solvent containing 2 /2 ml. of acetic acid were distilled out. Fifty ml. of a high-boiling, commercial aromatic solvent were added to the mixture. Subsequently, 10.5 grams of monomethyltriacetoxysilane (equivalent to 0.95 molecule of silane per silicon-bonded acetoxy group in the siloxanes) were added to the mixture. The resulting solution was applied to an aluminum panel. The coating air-dried tack-free to the touch in 15 minutes and was cured within four hours.
• dimethyldiacetoxysilane equivalent to one molecule of silane per silicon-bonded hydroxyl group
• Example 2 Sixty-six and two-thirds grams of resin A and 33 /3 grams of resin B, each added as a 50% by weight solution in xylene, were refluxed for 30 minutes with 9.5 grams of dimethyldiacetoxysilane equivalent to one molecule of silane per silicon-bonded hydroxyl group. Thirtyfive grams of solvent were distilled off from 133 to 145 C. containing the theoretical equivalent amount of acetic acid. This solvent was replaced with a high-boiling, commercial aromatic solvent and 10 grams of methyltriacetoxysilane equivalent to 0.84 molecule of silane per siloxane-silicon-bonded acetoxy group were added to the system.
• Example 3 Six hundred grams of resin A and 300 grams of resin B, each copolymer added as a 50% by weight solution in xylene, were mixed with 171 grams of dimethyldiacetoxysilane. equivalent to two molecules of silane per silicon-bonded hydroxyl group. This mixture was refluxed for 2 /2 hours after which 218 grams of distillate were removed in the range of from 110-135 C. This distillate contained the theoretical equivalent of acetic acid. The pot residue was found by infra-red analysis to contain no silicon-bonded hydroxyl groups.
• the pot residue was further diluted with a high-boiling commercial aromatic solvent to 50% solids. Four hundred grams of this solution were mixed with 20 grams of monomethyltriacetoxysilane equivalent to approximately .65 molecule of silane per siloxane-silicon-bonded acetoxy group. This mixture applied as a coating on redwood panels cured in 24 hours at room temperature in air.
• Example 4 When 100 grams of the following organopolysiloxanes are reacted with 44 grams of dimethyldiacetoxysilane by dissolving them in toluene and refluxing the system for one hour, the resulting products in each case, when mixed with methyltriacetoxysilane in amounts of from 25 grams to 132 grams do not gel or skin after having been stored in a capped container for more than two weeks. Coatings of these mixtures on steel, aluminum, plastic, ceramic and glass surfaces cure in less than six hours in air at room temperature. Coatings of these mixtures on wood surfaces cure within 24 hours in air at room temperature.
• Example 5 When any of the following silanes are substituted for the 9.5 grams of dimethyldiacetoxysilane in Example 2, mixtures having the same excellent shelf life and coating properties as the ultimate mixture of Example 2 are obtained.
• Example 6 When the following silanes are substituted for the 10.5 grams of monomethyltriacetoxysilane in Example 1, the resulting mixtures have a shelf life of' over two weeks and have essentially the same coating properties as the ultimate mixture of Example 1.
• a composition of matter consisting essentially of a solvent-soluble essentially hydroxyl-free organopolysiloxane having per silicon atom from 1.1 to 1.7 monovalent hydrocarbon radicals bonded to silicon through a carbon to silicon bond and containing silicon-bonded acyloxy radicals of less than four carbon atoms in amount equal to from one acyloxy radical per 100 silicon atoms to one acyloxy radical per three silicon atoms.
• composition of claim 1 with a monohydrocarbotriacyloxysilane in which each hydrocarbon radical contains less than four carbon atoms and each acyloxy radical contains less than four carbon atoms.
• a composition of matter consisting essentially of a solvent-soluble, essentially hydroxyl-free organopolysiloxane having per silicon atom from 1.1 to 1.7 monovalent hydrocarbon radicals bonded to silicon through a carbon to silicon bond of which from 0.25 to 1 radical per silicon is the phenyl radical and the remaining radicals are alkyl radicals of less than seven carbon atoms, said siloxane containing silicon-bonded acyloxy radicals of less than four carbon atoms in amount equal to from one acyloxy radical per 100 silicon atoms to one acyloxy radical per three silicon atoms.
• a composition of matter consisting essentially of a solvent-soluble esssentially hydroxyl-free organopolysiloxane having per silicon atom from 1.1 to 1.7 phenyl and methyl radicals of which from 0.25 to 1 radical is the phenyl radical, said siloxane containing silicon-bonded acyloxy radicals of less than four carbon atoms in amount equal to from One acyloxy radical per silicon atoms to one acyloxy radical per three silicon atoms.
• a method for stabilizing organopolysiloxane resins comprising reacting by heating in the range from 75 to C.
• a solvent-soluble, organopolysiloxane resin containing an average of from 1.1 to 1.7 monovalent hydrocarbon radicals bonded to silicon through a carbon to silicon bond per silicon atom and an average of from 0.01 to 0.333 hydroxyl radicals per silicon atom with

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Silicon Polymers (AREA)
• Paints Or Removers (AREA)

Priority Applications (4)

Applications Claiming Priority (1)

Publications (1)

Family

ID=24995872

Family Applications (1)

Country Status (4)

Cited By (4)

Families Citing this family (1)

Citations (5)

• 0
  • IT IT606679D patent/IT606679A/it unknown
• 1958
  • 1958-06-30 US US745246A patent/US3032529A/en not_active Expired - Lifetime
• 1959
  • 1959-05-11 FR FR794293A patent/FR1228519A/fr not_active Expired
  • 1959-06-11 GB GB20087/59A patent/GB862470A/en not_active Expired

Patent Citations (5)

Also Published As

Similar Documents